Chemistry Letters 2002
915
149 Hz. In the case of 2g the coupling constant changed to
578.8 Hz in D2O from 610.4 Hz in CDCl3 (Run 7).
This work was supported in part by a Grant-in-Aid for
Scientific Research from the Ministry of Education, Science,
Sports and Culture, Japan.
The X-ray molecular structure analysis of the potassium 18-
crown-6 selenothiophosphinic acid salt 2e was carried out.9
Although the quality of the crystal was not high and the position of
sulfur and selenium atoms was disordered, the structure of 2e
could be refined. The molecular structure of 2e is shown in Figure
1 along with selected bond lengths and angles. The salt 2e adopts a
monomeric structure. The K atom resides in the center of the 18-
crown-6 ether and is coordinated by the sulfur and selenium
atoms.
References and Notes
1
For a review: J. C. Tebby, D. G. Genov, and J. W. Wheeler, in
‘‘ComprehensiveOrganic FunctionalGroup Transformation,’’ ed. by A.
R. Katritzky, O. Meth-Cohn, and C. W. Rees, Pergamon, Oxford (1995)
Vol. 2, p 462.
2
For recent examples: W. E. Van-Zyl, J. M. Lopez-De-Luzuriaga, J. P.
Fackler Jr., and R. J. Staples, Can. J. Chem., 79, 896 (2001); S. V.
Larionov, V. G. Shchukin, L. A. Glinskaya, R. F. Klevtsova, and A. P.
Mazhara, Russ. J. Coord. Chem., 27, 463 (2001); J. E. Drake, M. B.
Hursthouse, M. Kulcsar, M. E. Light, and A. Silvestru, Phosphorus,
Sulfur Silicon Relat. Elem., 168 & 169, 617 (2001); V. Garcia-
Montalvo, A. Marcelo-Polo, R. Montoya, R. A. Tascano, S. Hernandez-
Ortega, and R. Cea-Olivares, J. Organomet. Chem., 623, 74 (2001); V.
Garcia-Montalvo, R. A. Tascano, A. Badillo-Delgado, and R. Cea-
Olivares, Polyhedron, 20, 203 (2001); J.-H. Park, P. O’Brien, A. J. P.
White, and D. J. Williams, Inorg. Chem., 40, 3629 (2001); S. Garcia-
Fontan, E. Lamas-Castro, P. Rodriguez-Seoane, and E. M. Vazquez-
Lopez, Acta Crystallogr., Sect. C, C57, 532 (2001); A. Silvestru, A.
Rotar, J. E. Drake, M. B. Hursthouse, M. E. Light, S. I. Farcas, R. Rosler,
and C. Silvestru, Can. J. Chem., 79, 983 (2001).
3
4
W. Kuchen and B. Knop, Angew. Chem., 76, 496 (1964).
H. Hertel and W. Kuchen, Chem. Ber., 104, 1735 (1971); H. Hertel and
W. Kuchen, Chem. Ber., 104, 1740 (1971); P. Christophliemk, V. V. K.
Rao, I. Tossidis, and A. Muller, Chem. Ber., 105, 1736 (1972); A.
¨
Mueller, V. V. K. Rao, and P. Christophliemk, J. Inorg. Nucl. Chem., 34,
345 (1972); S. Esperaꢀs and S. Husebye, Acta Chem. Scand., 27, 3355
(1973).
For multi-step synthesis of selenothiophosphinic acid salts: S. Kato, M.
Goto, R. Hattori, K. Nishiwaki, M. Mizuta, and M. Ishida, Chem. Ber.,
118, 1668 (1985).
Figure 1. ORTEP drawing of 2e with thermal ellipsoid plots
(50% probability). Hydrogen atoms were omitted for clarity. The
atoms E1 and E2 represent selenium or sulfur atom. Selected
5
ꢀ
interatomic distance (A) and bond angles (deg): P1–E1 2.082(1),
6
7
For synthesis of optically active selenothiophosphinic acid salt: Z.
Skrzypczynski and J. Michalski, J. Org. Chem., 53, 4549 (1988).
Typical experimental procedure for the synthesis of selenothiopho-
sphinic acid salts: To a suspension of KF (0.116 g, 2.00 mmol) and 18-
crown-6 ether (0.264 g, 1.00 mmol) in THF (5 mL) was added a solution
of 1d (0.377 g, 1.00 mmol) in THF (5 mL) at room temperature under Ar
atmosphere. The mixture was stirred under reflux in THF for 1.5 h. After
the addition of CH2Cl2 (20 mL), the insoluble parts were removed by
filtration, and the solventwas evaporated under reducedpressure(20 ꢂC,
120 Pa). To the residue was added Et2O (5 mL), and it was stirred for
10 min. The resulting precipitates were collected by filtration to give
0.544 g (94%) of 2e as a colorless solid. mp 202–204 ꢂC (dec); 1H NMR
(CDCl3): ꢀ 1.21 (d, 3JH{P ¼ 17:1 Hz, 9H, CH3), 3.60 (s, 24H, OCH2),
7.26–7.48 (m, 3H, Ar), 8.39–8.44 (m, 2H, Ar); 13C NMR (CDCl3): ꢀ
25.4 (d, 2JC{P ¼ 3:3 Hz, CH3), 37.8 (d, 1JC{P ¼ 44:7 Hz, CCH3), 70.0
P1–E2 2.113(1), P1–C1 1.841(4), P1–C2 1.873(4), E1ꢃ ꢃ ꢃK
3.319(1), E2ꢃ ꢃ ꢃK 3.4753(9), Oꢃ ꢃ ꢃK (ave.) 2.891; E1–P1–E2
117.26(5), E1–P1–C1 109.5(1), E1–P1–C2 106.8(1), E2–P1–C1
107.6(1), E2–P1–C2 109.3(1), C1–P1–C2 105.8(2), P1–E1–K1
90.60(4), P1–E2–K1 85.90(3), E1–K1–E2 63.58(2).
The reactivity of selenothiophosphinates 2 was elucidated
(Scheme 2). The reaction of 2h and 2i with methyl iodide
selectively took place at the selenium atoms of 2h and 2i to give
Se-methyl selenothiophosphinates 3 in high yields within 1 h. In
contrast, acylation of the salts 2h and 2i preferentially proceeded
at the sulfur atom to give mainly the products 4 along with a small
amount of the product 5.10
3
(OCH2), 126.1 (d, JC{P ¼ 11:6 Hz, Ar), 128.6 (Ar), 133.7 (d,
2JC{P ¼ 9:9 Hz, Ar), 138.4(d, 1JC{P ¼ 56:2 Hz, Ar);31P NMR(CDCl3):
ꢀ 74.8 (1JP{Se ¼ 607:4 Hz); 77Se NMR (CDCl3): ꢀ ꢁ128:4 (d,
1JSe{P ¼ 607:4 Hz); Anal. Calcd for C22H38KO6PSSe: C, 45.59; H,
6.61. Found: C, 45.31, H, 6.56.
8
9
Representative spectroscopic data of 1 measured in CDCl3: 1a: 31P
NMR ꢀ 54.0, 77Se NMR ꢀ ꢁ217:9, 1JP{Se ¼ 774:2 Hz; 1b: 31P NMR ꢀ
50.9, 77Se NMR ꢀꢁ209:7, 1JP{Se ¼ 763:7 Hz; 1c: 31P NMR ꢀ76.0, 77Se
NMR ꢀ ꢁ354:4, 1JP{Se ¼ 766:7 Hz; 1d: 31P NMR ꢀ 86.1, 77Se NMR ꢀ
ꢁ311:5, 1JP{Se ¼ 762:2 Hz.
Crystallographic data for 2e: C22H38KO6PSSe, fw ¼ 579:63, mono-
clinic, space group P21/n, a ¼ 10:650ð4Þ, b ¼ 16:682ð6Þ,
ꢂ
ꢀ
ꢀ 3
c ¼ 15:479ð6Þ A, ꢁ ¼ 91:973ð5Þ , V ¼ 2748ð1Þ A , Z ¼ 4, Dcalcd
¼
1:401 g cmꢁ3, T ¼ 193 K, R ¼ 0:102, Rw ¼ 0:141, 6293 reflections
(I > 3ꢂðIÞ). The selenium or sulfur atom appeared at the position [E(1)]
or at the position [E(2)] shown in Figure 1. The occupancy of the
selenium atom is 0.37 in [E(1)] and 0.63 in [E(2)], respectively, and the
reverse results are obtained for the sulfur atom.
Scheme 2. Reaction of ammonium salts 2 with CH3I and 4-
CH3C6H4COCl.
In summary, we successfully synthesized and characterized
selenothiophosphinic acid salts. Further studies on their applica-
tions as new metal ligands and as key precursors of selenothio-
phosphinic acids are in progress.
10 The starting salts 2 were also recovered, but the reaction at higher
temperatures did not necessarily gave the products in better yields
mainly because of the decomposition of the products formed.